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Efficient preparation of TMSCCl2Br and its use in dichlorocyclopropanation of electron deficient alkenes

Lee, Darren S.; Durán-Peña, Maria Jesus; Burroughs, Laurence; Woodward, Simon

Authors

Maria Jesus Durán-Peña

Laurence Burroughs

SIMON WOODWARD simon.woodward@nottingham.ac.uk
Professor of Synthetic Organic Chemistry



Abstract

The reaction of excess TMSCl and LiCCl2Br at low temperature is a technically simple high yield route to TMSCCl2Br. The latter is a stable source of the dichlorobromomethide carbanion, which undergoes 1,4-addition with cyclic nitroalkenes and (E)-fumarates leading to dichlorocyclopropanes after bromide explusion. For nitrostyrenes the reaction arrests at the 1,4-addition product. Low temperature NMR studies and DFT calculations suggest the formation of an ‘ate’ species [(nitronate)SiFMe3]- which, upon boil off of TMSF at 10 - 20 °C, yields the cyclopropane. DFT calculations also support the experimental differences between fluoride and acetate as promotors.

Citation

Lee, D. S., Durán-Peña, M. J., Burroughs, L., & Woodward, S. (in press). Efficient preparation of TMSCCl2Br and its use in dichlorocyclopropanation of electron deficient alkenes. Chemistry - A European Journal, 2016(22), doi:10.1002/chem.201600607

Journal Article Type Article
Acceptance Date Jan 1, 2016
Online Publication Date Apr 26, 2016
Deposit Date Apr 27, 2016
Publicly Available Date Apr 27, 2016
Journal Chemistry - a European Journal
Print ISSN 0947-6539
Electronic ISSN 1521-3765
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 2016
Issue 22
DOI https://doi.org/10.1002/chem.201600607
Keywords Dichlorocyclopropane, Michael Addition, Cyclopropanation, Conjugate Addition, Cyclopropane
Public URL http://eprints.nottingham.ac.uk/id/eprint/32995
Publisher URL http://onlinelibrary.wiley.com/doi/10.1002/chem.201600607/full
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingh.../end_user_agreement.pdf
Additional Information This is the peer reviewed version of the following article: Lee, D. S., Durán-Peña, M. J., Burroughs, L. and Woodward, S. (2016), Efficient Preparation of TMSCCl2Br and Its Use in Dichlorocyclopropanation of Electron-Deficient Alkenes. Chem. Eur. J.2016, 22., which has been published in final form at doi:10.1002/chem.201600607. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://eprints.nottingham.ac.uk/end_user_agreement.pdf





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